CN100336919C - Treatment method for manganese contained material by hydrometallurgy process - Google Patents
Treatment method for manganese contained material by hydrometallurgy process Download PDFInfo
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- CN100336919C CN100336919C CNB2003801006965A CN200380100696A CN100336919C CN 100336919 C CN100336919 C CN 100336919C CN B2003801006965 A CNB2003801006965 A CN B2003801006965A CN 200380100696 A CN200380100696 A CN 200380100696A CN 100336919 C CN100336919 C CN 100336919C
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- leach liquor
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- manganse dioxide
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- 238000000034 method Methods 0.000 title claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011572 manganese Substances 0.000 title claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 7
- 238000009854 hydrometallurgy Methods 0.000 title claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 229940075933 dithionate Drugs 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000005516 engineering process Methods 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 21
- 238000002386 leaching Methods 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- -1 iron ion Chemical class 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 235000010269 sulphur dioxide Nutrition 0.000 abstract 1
- 239000004291 sulphur dioxide Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 6
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical class OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
- C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Oceanography (AREA)
- Ocean & Marine Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for the hydrometallurgical processing of manganese containing materials, the process characterised by the combination of a manganese dioxide containing feedstock and an acidic solution to form a leach solution, and passing a volume of sulphur dioxide gas through that leach solution, whereby the levels of dithionate ion generated in the leach solution are less than about 5g/l. Also described is a process for the production of electrolytic manganese dioxide.
Description
Technical field
The present invention relates to the hydrometallurgical processes of manganese containing materials, particularly, can effectively utilize low-grade manganese dioxide raw material production manganese product, comprise electrolytic manganese dioxide by hydrometallurgical processes of the present invention.
Background technology
As everyone knows, can from the ore that contains Manganse Dioxide, refine manganese, still, in the extractive process, can produce the byproduct dithionic acid salt ion of concentration greater than 5 grams per liters with sulfurous gas.Along with this concentration of the increase of manganese refinement amount can obviously increase, reach that 20 grams per liters are quite a few to be seen.What is interesting is, put down in writing like this at " Advanced Inorganic Chemistry " the 3rd edition the 452nd page of Cotton and Wilkinson: " preparation dithionate or dithionic method are to react between sulfurous gas or sulphite and the Manganse Dioxide in the presence of the acid ".
Low-grade manganese dioxide raw material (manganese content is less than 40%) is general at present to adopt traditional roasting reduction, sulfuric acid leaching to produce manganous sulfate, and this method is uneconomical.Higher-grade Manganse Dioxide raw material (manganese content is greater than 40%) adopts the economy of this roasting-method of reducing also doubtful.At present the useful sulfurous gas method of from contain the Manganse Dioxide raw material, refining manganese can cause all that dithionate ionic concentration all need add " oxidation " or " slaking " operation of a costliness like this greater than 5 grams per liters in the solution in each Production Flow Chart.By " oxidation " dithionate ionic concentration is reduced to the process that is less than 1 grams per liter from 5 grams per liters and need spends long time, improved the occupation of capital.
The dithionic acid salts contg is poorly controlled in the manganous sulfate crystal product, causes product by the dithionic acid pollution by manganese, and this product can discharge sulfur dioxide gas by deferred reaction.
Therefore be necessary to adopt a kind of technology, refine manganous sulfate from the low-grade manganese dioxide raw material, dithionate ionic concentration is lower than 5 grams per liters in the leach liquor, preferably is lower than 1 grams per liter.
Recovery Manganse Dioxide will be avoided or can reduce required manganese ore exploitation and land destruction at least from low grade material, bring huge environmental benefit.The recycling of manganese residue can be saved limited resources.
In addition, adopt hydrometallurgical processes reduction Mn (IV), again do not need combustion gas kiln and fluidized-bed reactor, raw material does not need roasting to arrive about 1000 ℃ of coolings more yet before leaching.The demand of carbon significantly reduces, thereby has reduced the discharging of greenhouse gases.
The hydrometallurgy flow process is easy to control, just can show the dissolution degree of Mn (IV) by the solution potential of monitoring infusion solution or mud.Adopt the sulfurous gas lixiviation process to realize the fully conversion of Mn (IV), thereby avoided the residual of the manganese element that can leach in the solid slag to Mn (II).
When particularly producing electrolytic manganese dioxide (EMD), the raising of dithionic acid salt ionic concentration can influence quality and the purity of the EMD that generates in the electrolysis for production pond in the solution.Simultaneously, the discharge of hydrogen sulfide can bring some Occupational health and environmental problem.
The discussion of aforementioned background art is just in order to help the understanding of the present invention.What deserves to be mentioned is the mentioned data of these discussion before the application's priority date, is not to say it all is common knowledge in Australia.
At this paper, unless requirement is arranged in the literary composition in addition, word " comprises " or the various variations of its morpheme all are understood that to be used for being expressed as " including ", rather than expression " except ... contain ".
Summary of the invention
The invention provides a kind of hydrometallurgical processes of manganese containing materials, it is characterized in that a kind of raw material and a kind of acidic solution chemical combination that contains Manganse Dioxide forms a kind of leach liquor, feed a certain amount of sulfur dioxide gas, the dithionate ionic concentration in the leach liquor is lower than 5 grams per liters.
Preferably dithionate ionic concentration is lower than 1 grams per liter in the leach liquor.
Preferred pH of leaching solution maintains below 1.5.
A kind of mode of described hydrometallurgical processes is: contain the manganous sulfate that the mud that contains the Manganse Dioxide raw material that is lower than 10% (w/v) and concentration are lower than 120 grams per liters in the leach liquor, temperature is more than 95 ℃, and the pH value is lower than 1.5.
Described hydrometallurgical processes another kind of mode be: contain that manganese content is lower than 40% in the raw material of Manganse Dioxide.
Preferably, contain the soluble iron of starting point concentration greater than 4 grams per liters in the leach liquor, iron is with ferric sulfate (Fe
2(SO
4)
3) form exist.By the excessive or remaining Manganse Dioxide in the leacher ferrous ion concentration is remained on below 0.5 grams per liter.
In the whole leaching process, the ratio of monitoring iron ion and ferrous ion guarantees that redox potential (ORP) is more than or equal to 550mV (Ag/AgCl reference electrode relatively).
The time that sulfurous gas feeds leach liquor is no less than 10 hours, and is dissolved up to about 95% Manganse Dioxide.Preferred extraction time is 10 to 15 hours.
In case the sulfurous gas of Theoretical Calculation amount feeds in the leach liquor, 95% Manganse Dioxide is dissolved, and reaction just stops.
The present invention also provides a kind of technology of producing electrolytic manganese dioxide, it is characterized in that the raw material that contains Manganse Dioxide leaches in acidic solution, after feeding the sulfur dioxide gas of certain volume, dithionate ionic concentration maintains below 5 grams per liters, the leach liquor of gained is treated to become suitable electrolytic solution, gets off through electrolysis for production operation electrolytic manganese dioxide is precipitated again.
Preferably dithionate ionic concentration is lower than 1 grams per liter in the leach liquor.
Preferred pH of leaching solution maintains below 1.5.
A kind of mode of the technology of described production electrolytic manganese dioxide is: comprise concentration of hydraulic mixture in the leach liquor and be lower than the mud that contains the Manganse Dioxide raw material of 10%w/v and the manganous sulfate that concentration is lower than 120 grams per liters, temperature is more than 95 ℃, and the pH value is lower than 1.5.
The another kind of mode of the technology of described production electrolytic manganese dioxide is: contain that manganese content is lower than 40% in the raw material of Manganse Dioxide.
Preferably, contain the soluble iron of starting point concentration greater than 4 grams per liters in the leach liquor, iron is with ferric sulfate (Fe
2(SO
4)
3) form exist.By the excessive or remaining Manganse Dioxide in the leacher ferrous ion concentration is remained on below 0.5 grams per liter.
In the whole leaching process, the ratio of monitoring iron ion and ferrous ion guarantees that redox potential (ORP) is more than or equal to 550mV (Ag/AgCl reference electrode relatively).
The time that sulfurous gas feeds leach liquor is no less than 10 hours, and is dissolved up to about 95% Manganse Dioxide.Preferred extraction time is 10 to 15 hours.
In case the sulfurous gas of Theoretical Calculation amount feeds in the leach liquor, 95% Manganse Dioxide is dissolved, and reaction just stops.
Preferably, have at least a part to produce or remaining sulphuric acid soln in the acidic solution that leaching process uses from the electrolysis for production operation.Can in leach liquor, add acid if desired to guarantee that the pH value is lower than 1.5.
Description of drawings
The present invention only with formal description for example, comprises a specific embodiment and three accompanying drawings, wherein:
Fig. 1 is the present invention with the low-grade process flow diagram that contains manganese raw material production electrolytic manganese dioxide.
Fig. 2 describes the percentage ratio and the SO of the manganese that leaches in the extract technology shown in Figure 1 with graphics mode
2Relation between add-on, the Eh (solution potential).
The percentage ratio that Fig. 3 represents the manganese that leaches in time, SO
2The changing conditions of feeding amount.
Embodiment
The present invention shown in Figure 1 produces the technology 10 of electrolytic manganese dioxide, and a kind of manganese dioxide ore 12 that contains manganese about 34% grinds through a ball mill by wet process 14 earlier, and formed abrasive slurry is fed through the leacher 16 of a rare violent stirring device.
Except that abrasive slurry, also to add in the leacher 16 from the sulfuric acid electrolytic solution 17 of electrolysis for production operation 18 reuses, generate leach liquor.Feed the sulfur dioxide gas 20 of certain volume in leach liquor, sulfur dioxide gas 20 generates in sulfur burning operation 22, and sulphur burns in oxygen and generates sulfurous gas in this operation.
The concentration of hydraulic mixture that comes out from ball mill 14 is lower than 10% (w/v).The same with leach liquor, mud just is heated and stirs after entering leacher 16.Manganous sulfate (MnSO in the leach liquor
4) concentration less than 120 grams per liters, simultaneously the temperature of leach liquor is greater than 95 ℃, the pH value remains on below 1.5.
Leach liquor in the leacher 16 contains the soluble iron of starting point concentration greater than 4 grams per liters, and this soluble iron is with ferric sulfate (Fe
3(SO
4)
2) form exist.By the excessive or remaining Manganse Dioxide in the leacher ferrous ion concentration is remained on below 0.5 grams per liter.
Leaching will spend 10 to 15 hours time, and the sulfurous gas with certain volume in this process is passed in the leach liquor.The speed that feeds sulfurous gas in the leach liquor be decided by to enter in the mud of leacher 16 maximum 95% Manganse Dioxide can be in 10 to 15 hours dissolved required amount.The time of leaching also can be longer.
The ratio of iron ion and ferrous ion is by the monitoring of a redox potential (ORP) probe in the leacher 16, and the Schwellenwert of current potential is 500mV (an Ag/AgCl reference electrode relatively).If ORP is lower than 500mV, in leacher 16, add abrasive slurry.
The reaction of mainly carrying out in the leaching process is as follows:
MnO
2+SO
2＝MnSO
4
Generating manganous sulfate is principal reaction of the present invention, but still has the dithionate of trace to generate.Generating dithionate is the combination reaction of a free free radical:
SO
3 ·-+SO
3 ·-＝S
2O
6 2-
High pH value is the reason that promotes that dithionate generates.Therefore, the pH value in the leacher 16 must maintain below 1.5, and that mentions in as mentioned is the same.
After feeding the sulfurous gas 20 of Theoretical Calculation amount in the leach liquor, maximum 95% Manganse Dioxide can be dissolved, stops to lead to sulfur dioxide gas 20 in leacher 16, and reaction also stops thereupon.The sulfurous gas theoretical amount leaches the percentage ratio of manganese by Fig. 2 and the relation of Eh is calculated, and Fig. 2 shows the level of response that manganese (IV) can be accurately indicated in the variation of Eh or solution potential.Simultaneously Fig. 3 show leach manganese in the sulfurous gas feeding process percentage ratio over time.
Electrolytic manganese dioxide production technique 10 also comprises following operation: leach liquor makes the content of potassium and sodium be reduced to desired value by a jarosite chemical industry preface 22.By a pyrrhosiderite chemical industry preface 24, add water-ground limestone again, it is below horizontal to make the content of iron drop to ppm.Carry out solid/liquid separation then, comprise enrichment process 26 and filter operation 28.
Filter 28 gained solids through the residual manganese sulfate solution of washing and recycling, these solution are sent back to leacher 16, replenish that part of amount of the manganese sulfate solution 30 of discharging in the reuse electrolytic solution 17.The manganous sulfate of discharging in the solution 30 can be used for producing fertilizer.
The supernatant liquor of enrichment process 26 enters a vulcanization process 32 and removes heavy metal, comprises nickel, cobalt and molybdenum.Behind the vulcanization process 32, the sulfide of heavy metal is removed through pressure filtration 34, and the electrolytic solution of electrolysis for production operation 18 is stored in the storage tank 36.
Electrolysis for production operation 18 is at buried titanium anode, a piped cathode and do not have fully in the environment of wax and carry out.After production cycle through a fortnight, the attached product electrolytic manganese dioxide fines of having expired on the whole anode.Head product is packed after refining.
Technology of the present invention, especially leach the leach liquor dithionic acid salt ionic concentration that contains the manganese raw material in the operation and be lower than 5 grams per liters, preferably be lower than 1 grams per liter, can be used for handling the waste residue of the flue dust of the various ores that contain Manganse Dioxide (no matter grade height), mine tailing, fine ore, Ferro Manganese production equipment and waste residue, pelagite, ferromanganese tuberculosis, zinc smelting device and reclaim Manganse Dioxide in alkalescence or the carbon-zine cell.Adopt technology of the present invention to purify leach liquor that described raw material generates also is used to produce EMD, EMM (electrolytic manganese metal) and other manganic compound.
To the relevant speciality personnel is that surperficial improvement and variation also belongs to category of the present invention.
Claims (24)
1. the hydrometallurgical processes of a manganese containing materials, it is characterized in that containing Manganse Dioxide raw material and acidic solution chemical combination and form leach liquor, feed sulfur dioxide gas the pH value of described leach liquor is maintained below 1.5, and dithionate ionic concentration is lower than 5 grams per liters in the leach liquor.
2. technology as claimed in claim 1 is characterized in that: dithionate ionic concentration is lower than 1 grams per liter in the described leach liquor.
3. technology as claimed in claim 1 is characterized in that: the concentration of hydraulic mixture that contains the Manganse Dioxide raw material in the described leach liquor is lower than 10% (w/v), and the concentration of manganous sulfate is lower than 120 grams per liters, and temperature is more than 95 ℃, and the pH value is lower than 1.5.
4. technology as claimed in claim 1 is characterized in that: the described manganese content that contains the Manganse Dioxide raw material is lower than 40%.
5. technology as claimed in claim 1 is characterized in that: the starting point concentration of soluble iron is greater than 4 grams per liters in the described leach liquor.
6. technology as claimed in claim 5 is characterized in that: described iron is with ferric sulfate (Fe
2(SO
4)
3) the form existence.
7. 1 technology as claimed in claim is characterized in that: by the excessive or remaining Manganse Dioxide in the leacher described ferrous ion concentration is remained on below 0.5 grams per liter.
8. 1 technology as claimed in claim, it is characterized in that: in the whole leaching process, the ratio of monitoring iron ion and ferrous ion guarantees that redox potential (ORP) is more than or equal to 550mV.
9. 1 technology as claimed in claim, it is characterized in that: the time that feeds sulfurous gas in leaching process is no less than 10 hours, and is dissolved up to 95% Manganse Dioxide.
10. 1 technology as claimed in claim, it is characterized in that: extraction time is 10 to 15 hours.
11. 1 technology is characterized in that: in case in the sulfurous gas of the Theoretical Calculation amount feeding leach liquor, 95% Manganse Dioxide is dissolved, just reacts to stop as claimed in claim.
12. technology of producing electrolytic manganese dioxide, it is characterized in that the raw material that contains Manganse Dioxide leaches in acidic solution, feed the pH value that makes described leach liquor behind the sulfur dioxide gas and maintain below 1.5 and dithionate ionic concentration maintains below 5 grams per liters, pass through again that electrolysis for production operation electrolytic manganese dioxide is precipitated to get off.
13. technology as claimed in claim 12 is characterized in that: dithionate ionic concentration is lower than 1 grams per liter in the described leach liquor.
14. technology as claimed in claim 12 is characterized in that: described leach liquor, the concentration of hydraulic mixture that contains the Manganse Dioxide raw material is lower than 10% (w/v), and the concentration of manganous sulfate is lower than 120 grams per liters, and temperature is more than 95 ℃, and the pH value is lower than 1.5.
15. technology as claimed in claim 12 is characterized in that: the described manganese content that contains the Manganse Dioxide raw material is lower than 40%.
16. technology as claimed in claim 12 is characterized in that: the starting point concentration of soluble iron is greater than 4 grams per liters in the described leach liquor.
17. technology as claimed in claim 16 is characterized in that: described iron is with ferric sulfate (Fe
2(SO
4)
3) the form existence.
18. technology as claimed in claim 12 is characterized in that: described ferrous ion concentration is remained on below 0.5 grams per liter by the excessive or remaining Manganse Dioxide in the leacher.
19. technology as claimed in claim 12 is characterized in that: in the whole leaching process, the ratio of monitoring iron ion and ferrous ion guarantees that redox potential (ORP) is more than or equal to 550mV.
20. technology as claimed in claim 12 is characterized in that: the time that feeds sulfurous gas in leaching process is no less than 10 hours, and is dissolved up to 95% Manganse Dioxide.
21. technology as claimed in claim 12 is characterized in that: extraction time is 10 to 15 hours.
22. technology as claimed in claim 12 is characterized in that: in case the sulfurous gas of Theoretical Calculation amount feeds in the leach liquor, 95% Manganse Dioxide is dissolved, and reaction just stops.
23. technology as claimed in claim 12 is characterized in that: the described acidic solution that uses in leaching operation has at least a part to produce or remaining sulphuric acid soln from the electrolysis for production operation.
24. technology as claimed in claim 12 is characterized in that: add acid at home and abroad at leaching process and guarantee that pH of leaching solution is below 1.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2002952042 | 2002-10-10 | ||
| AU2002952042A AU2002952042A0 (en) | 2002-10-10 | 2002-10-10 | Hydrometallurgical processing of manganese containing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692169A CN1692169A (en) | 2005-11-02 |
| CN100336919C true CN100336919C (en) | 2007-09-12 |
Family
ID=28047615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801006965A Expired - Lifetime CN100336919C (en) | 2002-10-10 | 2003-10-01 | Treatment method for manganese contained material by hydrometallurgy process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7951282B2 (en) |
| CN (1) | CN100336919C (en) |
| AU (1) | AU2002952042A0 (en) |
| WO (1) | WO2004033738A1 (en) |
| ZA (1) | ZA200405429B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003903992A0 (en) * | 2003-07-30 | 2003-08-14 | Hitec Energy Limited | Improved hydrometallurgical processing of manganese containing materials |
| AU2004260809B2 (en) * | 2003-07-30 | 2008-11-20 | Auvex Resources Pty Ltd | Improved hydrometallurgical processing of manganese containing materials |
| BRPI0418064B1 (en) * | 2004-05-25 | 2013-07-30 | process for obtaining electrolytic manganese from ferroalloy waste | |
| AU2008303050B2 (en) * | 2007-09-26 | 2014-04-03 | Auvex Resources Pty Ltd | A micronutrient fertiliser and method for producing same |
| FR2946332B1 (en) * | 2009-06-05 | 2011-10-21 | Kimpe Sarl | PROCESS FOR PRODUCING MANGANESE OXIDE |
| WO2011085438A1 (en) * | 2010-01-13 | 2011-07-21 | Galaxy Resources Limited | Process for the production of electrolytic manganese dioxide |
| WO2012024294A1 (en) * | 2010-08-18 | 2012-02-23 | American Manganese Inc. | Processing of manganous sulphate/dithionate liquors |
| CN103261121B (en) * | 2010-12-08 | 2016-05-04 | 美萨矿物有限公司 | Improved micronutrient fertilisers and production method thereof |
| WO2013116290A1 (en) * | 2012-01-31 | 2013-08-08 | Drinkard Research And Development Corporation | Treatment of manganese-containing materials |
| CN102634819B (en) * | 2012-04-10 | 2015-05-13 | 四川大学 | Method for preparing electrolytic manganese/electrolytic manganese dioxide through leaching manganese oxide by sulfur dioxide |
| CN103572055A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of manganese sulfate for electrolytic manganese dioxide |
| CN108165742A (en) * | 2018-02-11 | 2018-06-15 | 乐昌市绿叶环保科技有限公司 | The method that dithionic acid manganese content is reduced in pyrolusite leachate |
| US20230174387A1 (en) * | 2020-05-07 | 2023-06-08 | Befesa Zinc Metal LLC | A method, a system, and an apparatus for preparing manganese sulfate |
| CN114505306A (en) * | 2021-12-30 | 2022-05-17 | 云锡文山锌铟冶炼有限公司 | Method for cleaning scale in sulfur dioxide reduction leaching kettle |
| WO2023148644A1 (en) * | 2022-02-04 | 2023-08-10 | Tata Steel Limited | A method for recovering manganese from manganese ore |
| CN115522053B (en) * | 2022-08-23 | 2023-07-25 | 郴州金铖环保科技有限公司 | Method for recovering tin, tungsten and manganese from wolframite leaching slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3211658A1 (en) * | 1982-03-30 | 1983-10-06 | Grillo Werke Ag | METHOD FOR DIGESTING MANGANESE BY MEANS OF SULFUR DIOXIDE |
| WO1998014623A1 (en) * | 1996-10-02 | 1998-04-09 | International Curator Resources Limited | Hydrometallurgical extraction of copper, zinc and cobalt from ores containing manganese dioxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3301777A (en) * | 1963-04-01 | 1967-01-31 | American Potash & Chem Corp | Anode for the electrowinning of manganese |
| US3438878A (en) * | 1966-10-27 | 1969-04-15 | Union Carbide Canada Ltd | Simultaneous refining of zinc and manganese dioxide |
| US5932086A (en) * | 1997-09-18 | 1999-08-03 | Elkem Metals Company, L.P. | Process for making manganese |
-
2002
- 2002-10-10 AU AU2002952042A patent/AU2002952042A0/en not_active Abandoned
-
2003
- 2003-10-01 WO PCT/AU2003/001295 patent/WO2004033738A1/en not_active Application Discontinuation
- 2003-10-01 CN CNB2003801006965A patent/CN100336919C/en not_active Expired - Lifetime
- 2003-10-01 US US10/501,277 patent/US7951282B2/en active Active
-
2004
- 2004-07-08 ZA ZA200405429A patent/ZA200405429B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3211658A1 (en) * | 1982-03-30 | 1983-10-06 | Grillo Werke Ag | METHOD FOR DIGESTING MANGANESE BY MEANS OF SULFUR DIOXIDE |
| WO1998014623A1 (en) * | 1996-10-02 | 1998-04-09 | International Curator Resources Limited | Hydrometallurgical extraction of copper, zinc and cobalt from ores containing manganese dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004033738A1 (en) | 2004-04-22 |
| CN1692169A (en) | 2005-11-02 |
| ZA200405429B (en) | 2005-06-20 |
| US7951282B2 (en) | 2011-05-31 |
| AU2002952042A0 (en) | 2002-10-31 |
| US20050103163A1 (en) | 2005-05-19 |
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